Method of staining glass with copper halide vapors



I Patented Oct. 7, 1947 with normal soda lime glass such as window glass v I 2,428,600 UNITED STATES PATENT OFFICE METHOD or s'mmmo amass wrrn COPPER HALIDE VAPORS No Drawing. Application March a, 1945, Serial No. 581,832

Claims. (CL 117-107) This invention relates to improvements in glass manufacture and more particularly to the production of copper stains on glass or the introduction of copper into glass surfaces. chloride atmosphere for varying lengths of time.

It is known that red glasses can be obtained by 5 e. g., from minutes to 8 hours. The copper the use of copper in two fundamentally different ions are thus introduced into the glass surface by ways. According to one method for producing the halide vapor treatment. The copper ions are a copper ruby, the copper compound is introduced thus introduced into the glass surface by-a base as an ingredient of the glass batch; and under exchange reaction with the sodium ions of the reducing conditions and in the presence of pro- 10 Glass. moting oxides glasses are obtained which give a deep ruby color on annealing or reheating.

can be varied, and products of varying properties and characteristics obtained. Thus, for example,

. tion, different results are obtained depending The other method called copper staining is upon the extent to which copper has entered the based on a base exchange between solid or molten glass surface and the conditions of reduction. If copper compounds and the alkali of the glass sur- )5 the amount of cuprous ions entering the glass face, this reaction being usually carried out by surface is sufficiently great, subsequent reduction coating the surface of the glassware or a part of will result in the production of a mirror. For this the surface with a mixture of a carrier substance purpose, the amount of cuprous ions entering the and a copper compound, first firing in an oxidizing glass surface should be as'great as possible and M atmosphere to cause the copper to replace alkali the depth of penetration is of secondary imporin the glass and subsequently firing under reductance. In other words, the concentration gradient of the cuprous ions should be high.

By obtaining a low concentration gradient, the formation of a red copper stain is favored rather or bottle glass and requires special glass composithan the production of a mirror. For the protions, particularly the presence of substantial duction of Y a mirror, ,the reduction is advantaamounts of potash. geously carried out at a high temperature and for According to the present invention, the vapors a short time, for example, at 700-800 0., by flash of volatile copper salts are caused to react with reduction With hydrogen of glass which has been hot glass surfaces. By using the vapors .of volag exposed to cuprous chloride vapors for 6 hours at ing conditions to develop a red glass. This copper staining method is not well adapted for use tile copper compounds it has been found that 550 C. At this high temperature the copper these react much more intensively than would be mirror forms within the surface of the ass a d expected from the action of the solid or molten does not dissolve in nitric acid. copper compounds in the so-called copper staining process. It has also been found that special glass compositions are not required and that ordinary or normal soda lime glass can be readily and successfully stained or colored. a sufliciently high concentration of cuprous ions.

It has been found that the vapors of both If the amount of copper combined with the surcupric and cuprous halides react with the hot 4 face is not sufficiently high, the ass on educglass surfaces. Different volatile copper comtion may not show a ruby color or metallic luster pounds can be used which in vapor form react but will nevertheless contain copper. with the glass at high temperatures with replace It is One advantage f t Present invention ment of alkali by copper, the copper ions migrating into the glass and replacing the alkali ions to be obtained with accurate control of the rewhich in turn migrate outof the glass. Cuprous suiting color. If'the reaction is allowed to take chloride is particularly advantageous as a. volatile place at a l temperature, around 0- copper compound in the process. 4 all color shades can be obtained, between a faint The process of the present invention is appli- P d a p red, depending p n the t e cable for the treatment of both soda and potash of exposure to the cuprous chloride vapor. By glasses. It is one advantage of the process that using fi p u s. around 500-550 C" it does not require special glass compositions and a strong r a n ta es place on the 8 8 s 11!- that it may readily be applied to normal or ordiface which leads to a high concentration of nary soda lime glasses such as window glass, botcuprous ions in the glass. Upon reduction, such tie glass, etc. a glass will not only develop a deep red color According to the present invention, the glass but it may also show a distinct metallic reflecsurfaces heatedto a high temperature are extion. This metal luster can be used for decoraposed to the vapors of cuprous chloride and adtive purposes and also as a basis for building up vantageously with subsequent reduction treatment. The temperature and time of treatment so tion, such as from Fehling solution with formalinto the glass surface and by reducing at lower temperatures, e. g., around 400 to 500 0., a copper ruby or metallic luster can be produced with the glass may be heated to 500 C. in a-cuprous On subjecting the thus-treated glass to reduc- By introducing a regulated amount of copperthat it enables products of different properties a layer of metallic copper by chemical deposi white bloom" on the glass surface.

dehyde or from alkaline copper phenylhydrazine solution. A heavy copper deposit in the form of a mirror can thus be obtained.

The invention is advantageously used for treating individual glass articles or objects for decorative purposes and for the formation of colored articles ranging in color from a faint pink to a deep red. Glass articles or surfaces can also be treated to adapt them for subsequent treatment to deposit copper or other metals thereon.

The invention will be further illustrated by the v following specific examples but it will be understood that the invention is not limited thereto:

Example I An article of normal or-ordinary soda lime glass was placedin a closed container together with solid cuprous chloride and the container with its contents was heated for 6 hours at 425 C. with access to air. volatilizes, producing an atmosphere of cuprous chloride vapor which comes into contact with the hot glass surfaces and. reacts therewith, the cuprous ions exchanging with the alkali ions of the glass forming. e. g., cuprous silicate -or complex silicates and sodium chloride which is not volatile at this temperature and deposits as a After such treatment the glass was cooled and washed and was colorless. on reduction in hydrogen at 460 C., it began to turn red in a few minutes and when removed from the furnace after 30 minutes had a medium red color and no metallic luster.

Example [I A similar glass article was exposed to cuprous chloride vapor at the same temperature (425 C.) for 24 hours and reduced under the same conditions (in hydrogen at 460 C.) and the resulting article had a more intense red color and a little metallic luster.

Example In A normal soda lime glass was exposed to cuprous chloride vapor for 1 hour at 550 C., and then reduced inhydrogen at 460 C., for a few minutes. The glass was colorless before reduction and had a medium red color and no metallic reflection after reduction.

I Example IV A normal soda lime glass was exposed to cuprous chloride vapor for 6 hours at 550? C., and

' had a light blue color before reduction. After reduction in hydrogen at 460 C., it had a dark red color and a pronounced metallic reflection.

Example v mal soda lime glasses as well as to other special glasses such as those containing substantial amounts of potash. The process also has the advantage that it enables an accurate control of the resulting color to be obtained. Thus, if the reduction is allowed to take place at a low .tem-

The cuprous chloride perature, around 350-425 0.. varying color shades can be obtained, as above pointed out, from a faint pink to a deep red, depending upon the time of exposure; while at higher temperatures, around 500-550 C., a strong reaction takes place on the glass surface which leads to a high concentration of copper ions in the glass and upon reduction such a glass will develop-a deep red color and may also show a distinct metallic 10 reflection. It will thus be seen that the present invention provides an improved process for treating glass and glass articles to incorporate copper therein for decorative purposes and also for subsequent building up of metallic copper thereon. Where a copper mirror is formed by the process it differs from a layer of metallic copper on the glass I which can be dissolved in nitric acid in that the copper mirror forms within the surface of th glass and is resistant to dissolving in nitric acid.

Iclaim: 1 I 1. The method of staining glass with copper which comprises subjecting a hot, alkali-contain.- ing glass surface to the action of vapors of a volatile copper halide which will react with the alkali of the glass surface with replacement of alkali ions of the glass with copper ions. and subsequently subjecting the glass containing copper within the glass surface to reduction with hydrogen at an elevated temperature.

2. The method of treating glass with copper which comprises subjecting hot, alkali-containing glass surfaces to the action of vapors of cuprous chloride with resulting replacement of alkali ions of the glass with copper ions, and subsequently subjecting the glass containing copper within the glass surface to reduction withhydrogen at an elevated temperature.

3. The method of producing glass colored by 40 copper which comprises subjecting alkali containing glasses to the action ofvapors of cuprous chloride at a temperature around 350-425" C., and

subsequently reducing the resulting glass with hydrogen at an elevated temperature.

copper which comprises subjecting alkali containing glasses to the action of vapors of cuprous t 4. The method of producing glass colored by I chloride at a temperature around 500-550 ,C., and subsequently reducing the resulting glass 5 f with hydrogen at an elevated temperature.

5. The method of treating alkali containing glasses which comprises subjecting the same at a temperature of about 350to 550 C.to cuprous chloride vapors and continuing such treatment 5 for a suflicient time to cause copper ions to replace alkali ions in the glass to an extent sufllcient to give a. colored glass product and subsequently subjecting the product to reduction with I hydrogen at a. high temperature.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STA'IES rA'rE Ts Date Number Name 1,183,109 Parsche May 16, 1916 1,372,258 Tomlinson Mar. 22, 1921 1,497,417 Weber June 10, 1924 1,816,476 Fink et al July28, 19.31 

